Mechanistic Investigation of Molybdate-Catalysed Transfer Hydrodeoxygenation

Autor:	Daniel Bo Larsen, Ayele Teshome, Johannes Rytter Dethlefsen, Peter Fristrup, Allan Robertson Petersen
Rok vydání:	2016
Předmět:	inorganic chemicals 010405 organic chemistry Organic Chemistry Disproportionation Isopropyl alcohol General Chemistry 010402 general chemistry 01 natural sciences Medicinal chemistry Toluene Catalysis 0104 chemical sciences Solvent Benzaldehyde chemistry.chemical_compound chemistry Benzyl alcohol Organic chemistry Bibenzyl Hydrodeoxygenation
Zdroj:	Chemistry - A European Journal. 22:16621-16631
ISSN:	0947-6539
DOI:	10.1002/chem.201603028
Popis:	The molybdate-catalysed transfer hydrodeoxygenation (HDO) of benzyl alcohol to toluene driven by oxidation of the solvent isopropyl alcohol to acetone has been investigated by using a combination of experimental and computational methods. A Hammett study that compared the relative rates for the transfer HDO of five para-substituted benzylic alcohols was carried out. Density-functional theory (DFT) calculations suggest a transition state with significant loss of aromaticity contributes to the lack of linearity observed in the Hammett study. The transfer HDO could also be carried out in neat PhCH2OH at 175 °C. Under these conditions, PhCH2OH underwent disproportionation to yield benzaldehyde, toluene, and significant amounts of bibenzyl. Isotopic-labelling experiments (using PhCH2OD and PhCD2OH) showed that incorporation of deuterium into the resultant toluene originated from the α position of benzyl alcohol, which is in line with the mechanism suggested by the DFT study.
Databáze:	OpenAIRE
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